Catalytic enantioselective carbon-carbon bond formation involving simple alkenes without heteroatom function groups represents a highly desirable but formidable synthetic task. Aside from the long-known asymmetric cyclopropanation catalyzed by various late transition metal complexes, the currently known reactions of this class, including asymmetric carbonyl ene reaction, asymmetric hydroformylation, and asymmetric hydrocyanation, have been reported only within the last several years. It should also be noted that the scope of the carbonyl ene reaction is essentially limited to 1,1-dialkylsubstituted alkenes, and that of the latter two appears to be limited to vinylarenes.